Dodecyl 2-hydroxyethyl sulfoxide

ABSTRACT

HAS UTILITY IN DETERGENT COMPOSITIONS AS A FOAM-STABILIZING ADDITIVE. C12H25-SO-(CH2)2-OH   THE COMPOUND DODECYL 2-HYDROXYETHYL SULFOXIDE

United States Patent 3,739,031 DODECYL Z-HYDROXYETHYL SULFOXIDE Hill M.Priestley, North Bergen, and James H. Wilson, Demarest, N01, assignorsto Lever Brothers Company, New York, N.Y.

No Drawing. Division of application Ser. No. $69,985, Aug. 25, 1969,which is a continuation of application Ser. No. 647,333, June 20, 1967,which is a continuation-in-part of application Ser. No. 365,487, May 6,1964, which in turn is a continuation-in-part of applications Ser. No.725,505, Apr. 1, 1958, and fier. No. 60,546, Oct. 5, 1960, all nowabandoned. This application Oct. 23, 1970, Ser. No. 83,623

Int. Cl. C07c 147/14, 147/02 U.S. Cl. 260607 A 1 Claim ABSTRAiIT OF THEDISCLOSURE The compound dodecyl Z-hydroxyethyl sulfoxideOIZH2ES-CHZCH2OH has utility in detergent compositions as afoam-stabilizing additive.

This application is a divisional of co-pending application Ser. No.869,985, filed on -Aug. 25, 1969, which is a streamlined continuation ofapplication Ser. No. 647,333 filed June 20, 1967 and now abandoned,which in turn was a continuation-in-part of application Ser. No. 365,487filed May 6, 1964, also now abandoned, which in turn was acontinuation-in-part of our applications Ser. Nos. 725,505 filed Apr. 1,1958, and 60,546, filed Oct. 5, 1960, now abandoned.

The present invention relates to novel dialkyl monosulfoxides andrelated compounds which are useful either as detergents and foamstabilizers or as intermediates in the preparation of compounds whichare useful as detergents and foam stabilizers.

Alkyl sulfoxides having a long chain fatty acid residue are known tohave surface active properties. U.S. Pat. No. 2,787,595 to Webbdiscloses the use of alkyl sulfoxides as the essential active ingredientin detergent compositions-According to Webb, the sulfoxides may beemployed per se as the essential active ingredient in detergentcompositions, but preferably are employed in combination with inorganicbuilder salts. It is also stated in the patent that other syntheticdetergents may be employed as detergency supplements in combination withthe sulfoxides and that foam stabilizers may be added.

It is common practice in the industry to include foam stabilizers indetergent compositions to improve the persistence and stability of thefoam produced by agitation of the washing solution containing thedetergent composition. These foam stabilizers are particularly useful indetergent compositions based upon organic non-soap synthetic detergentcompounds.

In accordance with the present invention, novel compounds are providedfrom the group consisting of dodecyl glyceryl sulfoxide,dodecycloxyethyl methyl sulfoxide, dodecyl acetonyl sulfoxide, dodecyl2-chloroethyl sulfoxide, dodecyl Z-hydroxyethyl sulfoxide,dodecyloxyethoxyethyl methyl sulfoxide, dodecyl 2-iodoethyl sulfoxide,dodecyl Z-mercaptomethylethyl sulfoxide, dodecyl 2- (Z-hydroxy)ethoxyethyl sulfoxide, dodecyl Z-methoxyethyl sulfoxide, dodecylZ-ethoxyethyl sulfoxide, dodecyl 2-allyloxyethy1 sulfoxide, dodecylacetonyl sulfide, do-

sulfide, and dodecyloxyethoxyethyl chloride.

The specific compounds of this invention are:

Dodecyl glyceryl sulfoxide Dodecyloxyethyl methyl sulfoxideC1ZH25OCHZCH2SOCH3 Dodecyl acetonyl sulfoxide C H SOCH COCH Dodecyl2-chloroethyl sulfoxide Dodecyl Z-hydroxyethyl sulfoxideC12H25S\OCH2CH2OH Dodecyloxyethoxyethyl methyl sulfoXide C H OCH CH OCHCH SOCH Dodecyl 2-iodoethyl sulfoxide C H SOCH CH I DodecylZ-mercaptomethylethyl sulfoxide C1ZHZ5SOCH2CHZSCH3Dodecyl-Z-(Z-hydroxy)ethoxyethyl sulfoxide C H SOCH CH OCH CH OH DodecylZ-methoxyethyl sulfoxide C H SOCH CH OCH Dodecyl 2-ethoxyethyl sulfoxideC H SOCH CH OC H Dodecyl 2-allyloxyethyl sulfoxide C H SOCH CH=CHDodecyl acetonyl sulfide C H SCH COCH Dodecyloxyethyl methyl sulfideC12H25OCH2CH2SCH3 Dodecyloxyethoxyethyl methyl sulfideC1QHZ5OCH2CHZOCHZCHZISCH3 Dodecyloxyethoxyethyl chlorideC12H25OCH2CH2OCH2CH2C1 A preferred class Within the above describedsulfoxides I include dodecyl glyceryl sulfoxide,

C H SOCH CHOHCH OH dodecyloxyethyl methyl sulfoxide,

C H OCH CH SOCH and dodecyloxyethoxyethyl methyl sulfoxide,

C H OCH CH OCH CH SOCH These materials are exceptionally suitable in thepresence of household bleach.

Another preferred class Within the broad class described above aredodecyl 2-chloroethyl sulfoxide,

and dodecyl 2-iodoethyl sulfoxide, C H SOCH CH I. These compounds areuseful as intermediates in the preparation of a wide variety of othersulfoxides having the aforementioned desired properties.

It has been found that the presence of small amounts of the sulfoxidesdescribed above improve the stability of the foam produced by agitatingaqueous solutions of suds-producing materials selected from the groupconsisting of anionic, ampholytic and nonionic organic syntheticdetergents. Certain of the sulfoxides, as well as the sulfides andchlorides are useful in preparing known or novel sulfoxides which are inturn useful as detergents and suds boosters.

The following table lists the novel compounds of this invention togetherwith their formula, their melting point and the melting point of thecorresponding sulfone.

TABLE I Melting Compound Melting point point, of sul- Number NameFormula C. fone, C.

1 Dodecyl glyoerly sulioxide C12H25S0CH2CHOHGH2OH 83 93 2..Dodeeyloxyethyl methyl sulfoxide. C1zHz OCHzCH2SOCH 43 66 3 Dodecylacetouyl sulfoxide 01211:: 2C0 O a 84 81 4.. Dodecyl 2-ehloroethylsulfoxide. C12H25SOCH CH2Cl 75 62 5 Dodecyl 2-hydroxyethyl sulfoxideC12HZ SOCH2CH2OH 71 6 Dodeoyloxyethoxyothyl methyl sulfox1de. 0111120CHzCHzOCHzOHzSOCH; 43 44 7 odccyl 2-iodoethyl sulfoxi e C12H25SOCH2CH2I74 100 8.- Dodecyl Z-mercaptomothylethyl sulfoxide C12H25SOCH2CH2SCH3 681 71 9 r)odecyl-2-(2-hydroxy)othoxyethyl sulfoxid C1ZH-,SO CHzCHzOCII2CHzOH 54 60 10 Dodecyl Z-methoxyethyl sulioxidc CHHQfiOOHZCHZOCIh 5848 11 Dodecyl Z-othoxythyl sulfoxide C12Hz SOGH2CII20C H 57 47 12Dodecyl 2-allyloxyethyl sulfoxide C12H25SOCH2CH2O CHzCH=CHz 54 46Boiling point, C.

Dodecyl acetonyl sulfide Ci2H25SCH2COCH3 150-160/L0 mm.

Dodecyloxyethyl methyl sulfide C H2 OCH2OH2SCH 140/1.0 mm.

. Dodeeyloxyethoxyethyl methyl sulfid Ci2H25OCHzCH2O CHzCHzSCH 155/115mm Dodecyloxyethoxyethyl chloride C1zHz5OCH2CHzOCHzCH2Cl 150/l.5 mm

1 M.P. oi disulione, 171 0.

Of the 12 sulfoxides listed in Table I, Nos. 1, 2, 3, 5 C H SOCH CHCl+NaOC H and 6 were prepared by the oxidation of the correspondingsulfides with concentrated nitric acid or with hydrogen peroxide inaccordance with the following:

(b) ++S+ HZOZ=+S O-(:) H2O The sulfides, in turn, had been obtained bywarming an alcoholic solution of the sodium mercaptide with a halide:

-(:JSNa 01-( h:(:3SC: NaOl Thus, sodium dodecyl mercaptide when treatedwith glycerol alphamonochlorohydrin, gave dodecyl thioglyceryl ether;with chloroacetone, dodecyl acetonyl sulfide; and with ethylenechlorohydrin, dodecyl 2-hydroxyethyl sulfide:

(The dodecyl 2-hydroxyethyl sulfide had also been prepared from C HBr+NaSCH CH OH) Dodecyl acetonyl sulfide, C H SCH COCH is novel.Similarly, sodium methyl mercaptide, when treated with dodecyloxyethylchloride yielded dodecyloxyethyl methyl sulfide; anddodecyloxyethoxyethyl chloride gave dodecyloxyethoxyethyl methylsulfide:

CH SNa+ClCH CH OC H =C H OCH CH SCH NaCl CH SNa+ClCH CH OCH CH OC H =C HOCH CH OCH CH SCHfi-NflCl Both sulfides and the dodecyloxyethoxyethylchloride, C H OCH CH OCH CH Cl, are novel.

The dodecyl 2-chloroethyl sulfoxide was prepared by oxidation of theknown dodecyl 2-chloroethyl sulfide with sodium hypochlorite and withnitric acid:

=C H SOCH CH Cl+2 NO +H O Since this sulfoxide is also a halide, it canenter into reaction with sodium mercaptides and alcoholates, to yieldnew compounds which already contain a sulfoxide group:

In this manner, there was prepared, reading the right hand formulasabove from top to bottom: dodecyl 2-mercaptomethylethyl sulfoxide,dodecyl 2-(2-hydroxy)ethoxyethy1 sulfoxide, dodecyl Z-methoxyethylsulfoxide, dodecyl 2- ethoxyethyl sulfoxide, and dodecyl 2-allyloxyethylsulfoxide.

For the preparation of the known dodecyl vinyl sulfoxide, C H SOCH=CH bya new procedure, i.e. by removal of hydrohalide from dodecyl 2-haloethylsulfoxide 01211253 0 C CE,

I HH 2. more reactive halide was desired. This was achieved by refluxingdodecyl 2 chloroethyl sulfoxide with sodium iodide in acetone solution,whereby dodecyl 2-iodoethy1 sulfoxide was formed:

dodecyl acetonyl sulfide C H SCH COCH dodecyloxyethyl methyl sulfide C HOCH CH SCH},

dodecyloxyethoxyethyl methyl sulfide C H OCH CH OCH CH SCHdodecyloxyethoxyethyl chloride C H OCH CH OCH CH Cl EXAMPLE 1 Dodecylacetonyl sulfide, C H SCH COCH To a mixture of 101 g. dodecyl mercaptanand 300 m1. 3A alcohol,

there was added, with stirring, a solution of 22 g. sodium hydroxide in30 ml. of distilled water. The sodium mercaptide solution was thentreated with 51 g. chloroacetone, a few grams at a time, with coolingand stirring. The mixture was allowed to stand at room temperature forhalf and hour, and then poured into two liters of water. The oil wasextracted with 400 ml. ether, the ether solution washed with water, anddried over anhydrous sodium sulfate. The solvent was distilled off, andthe residue fractionated. The yield of dodecyl acetonyl sulfie was 86 g.(67% of the theory), B.P. 155-160 C./1.0 mm. (bath temp. 195 0.). Thephenylhydrazone derivative melted at 43 C.; the oxime was an oil; andthe semicarbazone melted at 81 C.

Dodecyl acetonyl sulfoxide, C H SOCH COCH .A solution of 5.0 gramsdodecyl acetonyl sulfide in 30 ml. acetone was treated with 1.75 ml. of30% hydrogen peroxide. The solution was refluxed for minutes on a waterbath kept at 60 C. The reaction mixture was freed of the solvent byvacuum evaporation with a water pump on a water bath at 40 C. The solidresidue was triturated with 50 ml. Skellysolve B in a mortar andfiltered by suction. The material on the filter Was washed with 10 ml.light petroleum ether. The yield of the sulfoxide was 4.1 grams, 75% oftheory, and it had a melting point of 84 C. One gram, afterrecrystallization from 40 ml. Skellysolve B, yielded 0.85 gram of aproduct having a melting point of 84 C.; phenylhydrazone, melting point73 C.

The ketosulfoxide is soluble in aqueous sodium hydroxide solution, inwhich it foams exceedingly. On acidification, the ketosulfoxide isrecovered unchanged. Dodecyl acetonyl sulfoxide is much more stable instrong alkali than is the corresponding ketosulfone. Thus, theketosulfoxide is recovered unchanged by refluxing it in 10% sodiumhydroxide for 4 hours. A solution of dodecyl acetonyl sulfoxide in 10%aqueous sodium hydroxide was kept unchanged in the 52 C. oven for twoweeks.

EXAMPLE 2 As was mentioned above, it was in the course of thepreparation of the known dodecyl vinyl sulfoxide by a new route, thatthe following three new sulfoxides were obtained:

Dodecyl 2-hydroxyethyl sulfoxide, C H SOCH CH OH Dodecyl 2-chloroethylsulfoxide, C H SOCH CH CI Dodecyl 2-iodoethyl sulfoxide, C H SOCH CH I IThe reactions mvolved are as follows:

Dodecyl 2-hydroxyethyl sulfide, C H SCH CH OH.- Metallic sodium, 23 g.,was dissolved in 410 ml. 3A, 95% alcohol, and to this was added 78 g. of2-mercaptoethanol, HSCH CH OH. There was then introduced 249 g. dodecylbromide, dropwise, with stirring. Heat was evolved. The mixture wasrefluxed for half an hour. Analysis showed that no mercaptide waspresent and that this time interval had been sufficient for completionof the reaction. The product was extracted with 500 ml. ether, theethereal solution washed 5 times with water, and dried (sodium sulfate).The ether was removed, and the residue vacuum distilled, with steampassing through the condenser jacket. There was obtained 229 g. ofdodecyl 2-hydroxyethyl sulfide, B.P. 177 C./2.5 mm. (oil bath temp. 220C.).

Dodecyl 2-chloroethyl sulfide, C H SCH CH Cl.- Thionyl chloride, 128ml., was added, with cooling and stirring, to a mixture of 70 ml.pyridine and 228 g. dodecyl 2-hydroxyethyl sulfide. At first, theaddition was slow, being guided by the amount of heat evolved. Later, asthe heat of reaction declined, the addition was more rapid. The mixturewas then heated, with stirring, at 120 C. for 1.5 hours. Excess thionylchloride was decomposed by the addition of 100 ml. water at 60 C. Theproduct was extracted with 500 ml. ether, washed with water, and driedovernight with anhydrous sodium sulfate. After removal of the ether onthe water bath, the residue was heated on an oil bath under the vacuumof a water pump. The intermediate chlorosulfinate, C H SCH CH OSOCl, isquite stable, and was heated at 200 C. under reduced pressure to driveout all of the sulphur dioxide, leaving behind the dodecyl 2-chloroethylsulfide. This was fractionated, giving 149 g., B.P. 172 C./2.0 mm. (bathtemp. 222 C.).

Dodecyl 2-chloroethyl sulfoxide, C H SOCH CH Cl.- Dodecyl 2-chloroethylsulfide, 50 g., was added in small portions, with cooling and stirringto ml. concentrated nitric acid. The product was poured into 800 ml.water. Filtration was slow, hence the suspension was centrifuged. Thesupernatant liquid was decanted, the residual product stirred up withwater in the centrifuge tubes, and recentrifuged. This was repeated,using as a wash 50% 3A alcohol. The solid was finally filtered on aBuchner funnel, and dried. The yield of doecyl 2-chloroethyl sulfoxidewas 48 g., M.P. 75 C.

Dodecyl-Z-chloroethyl sulfone, C H SO CH CH CL The sulfone derivativeshad been prepared from the sulfide by treatment with excess hydrogenperoxide in glacial acetic acid. The mixture was ether refluxed for oneor two hours, or allowed to stand at room temperature for 48 hours. Asan example, the preparation of dodecyl 2-chloroethyl sulfone isdescribed. Dodecyl 2- chloroethyl sulfide, 10 g., was mixed with ml.glacial acetic acid and 40 ml. of 30% hydrogen peroxide. The sulfide hadnot all dissolved, and an oil was present. The mixture was refluxed for1.5 hours. Initially, the oil was still present at the refluxtemperature, but afterwards, a homogeneous solution was obtained. Oncooling the solution, the sulfone crystallized out. It was filtered,washed with 10 ml. glacial acetic acid and then with 4 ml. distilledwater. The yield of dry dodecyl 2-chloroethyl sulfone was 8.4 g., M.P.62 C.

Dodecyl 2-iodoethyl sulfoxide, C H SOCH CH I.- A mixture of 40 g.dodecyl 2-chloroethyl sulfoxide (this sample had been freed of traces ofnitric acid by washing with bicarbonate solution to alkalinity), 45 g.sodium iodide, and 30 ml. acetone was refluxed for 5 hours. The acetonesolution was decanted from the sodium chloride, and the salt rinsed witha little acetone. The combined acetone solution was refluxed for anadditional 7 hours. Most of the acetone was evaporated. The residue wastreated with water, filtered, and the moist solid was recrystallizedfrom 200 1111. 3A alcohol. There was obtained 28.4 g. of dodecyl2-iodoethyl sulfoxide, M.P. 74 C.

Dodecyl vinyl sulfoxide, C H SOCH:CH .A suspension of 5.0 g. dodecyl2-iod0ethyl sulfoxide in 25 ml. 10% sodium hydroxide was heated at 80C., with stirring, for two hours. The mixture was poured into 300 ml.ice Water. After an hour, the solid was filtered, washed with water, anddried. The yield of dodecyl vinyl sulfoxide was 3.2 g., M.P. 42 C.

Dodecyl Z-hydroxyethyl sulfoxide,

H a ZCH OH Dodecyl 2-hydroxyethyl sulfide, 9.0 g., was gradually addedto 10 ml. concentrated nitric acid, with cooling and stirring. Ice waterwas introduced, and the suspension was extracted with 100 ml.chloroform. This was washed with water, then with sodium bicarbonatesolution, and

again with water. The chloroform solution was dried with sodium sulfate.Evaporation of the solvent left behind 9.2 g. solid, which wasrecrystallized from 70 m1. Skellysolve B. The yield of dodecylZ-hydroxyethyl sulfoxide was 7.8 g., M.P. 71 C.

Dodecyl 2-mercaptomethylethyl sulfoxide,

Metallic sodium, 1.15 g., was dissolved in 50 ml. ethyl alcohol, and tothe cooled solution was added 4 ml. of condensed methanethiol, C-I-I SH,and 14.0 g. dodecyl 2- chloroethyl sulfoxide. The suspension was heatedon the water bath at 60 C. for 15 minutes. A test sample, titrated withstandard acid (phenolphthalein) showed that the reaction was complete.The reaction product was poured into 500 ml. water, the solid filtered,and dried. The yield of dodecyl Z-mercaptomethylethyl sulfoxide was 14.4g., M.P. 67 C. The product was halogen-free. One gram was recrystallizedfrom 4 ml. ethyl alcohol, giving 0.8 g., M.P. 68 C.

Dodecyl Z-ethoxyethyl sulfoxide,

When the above reaction was repeated, except that the methanethiol wasomitted, there was obtained dodecyl 2-ethoxyethyl sulfoxide, M.P. 58 C.Similarly, dodecyl 2-methoxyethyl sulfoxide was obtained when thesolvent was methanol, and dodecyl 2-allyloxyethyl sulfoxide, when thesolvent was allyl alcohol.

Dodecyl 2- (2-hydroxy)ethoxyethyl sulfoxide,

C QH SSOCH CH OCH CH OH Metallic sodium, 0.23 g., was dissolved in ml.ethylene glycol, and to this was added 1.0 g. dodecyl 2-chloroethylsulfoxide. The mixture was heated at 80 C. for minutes. A homogenoussolution resulted. This was poured into 60 ml. cold water. The solid wasextracted with 100 ml. ether, the ether solution was washed with water,dried with sodium sulfate, and the ether distilled. There was obtained0.7 g. dodecyl-2-(2-hydroxy)ethoxyethyl sulfoxide, M.P. 54 C.

EXAMPLE 3 Dodecyl glyceryl sulfoxide, compound No. 1 in the table wasprepared from dodecyl thioglyceryl ether, C H SCH CHOHCH OH. The lattercompound was in turn prepared according to a modification of theteachings of U.S. Pat. No. 1,978,526. To a solution of 5.2 gramsmetallic sodium in 130 ml. of ethyl alcohol, 95%, there was added 45grams dodecyl mercaptan followed by 24.6 grams glycerylalpha-monochlorohydrin. The mixture was refluxed for one hour on a waterbath, and then poured into water. The product was extracted with 400 ml.of diethyl ether, washed with a sodium chloride solution and dried overanhydrous sodium sulfate. The ether was distilled off. The residueamounted to '54 grams and had a melting point of 47-48 C. A solution of26 grams of the crude thioglyceryl ether in 260 ml. of diethyl ether wascooled in ice. The crystals were filtered and washed with 50 ml. coldether. The yield of pure dodecyl thioglyceryl ether, melting point 52C.,was 15.3 grams.

The compound was also prepared from l-dodecene and alpha-thioglycerol,according to the equation:

A mixture of 421 g. l-dodecene (2.5 moles), 300 g. of commercialalpha-thioglycerol, assay 90% (2.5 moles), and 1.26 g. alpha,alpha-azodi-isobutyronitrile was heated on the water bath at 90 C., withstirring. After minutes, the temperature rose to 125 C. The water bathwas removed, and the reaction mixture was allowed to cool to 70 C. Itwas then poured, with stirring, into 4 liters of n-hexane. A completesolution resulted. The

mixture was cooled in ice, the solid filtered off, and washed with 200ml. cold n-hexane. The yield of dodecyl thioglyceryl ether, M.P. 51 C.,was 450 g. (65% of the theory).

Dodecyl glyceryl sulfoxide (A).-Powdered dodecyl thioglyceryl ether, 5.0g., was slowly added at room temperature to 25 ml. of concentratednitric acid. This was treated with ice water, the solid filtered, washedwith water, and dried. The yield of dodecyl glyceryl sulfoxide was 5.2g., M.P. 83 C.

Dodecyl glyceryl sulfoxide (B).-To a solution of 100 g. of dodecylthioglyceryl ether in 600 ml. acetone there was slowly added, withcooling and stirring, 50 ml. of 30% hydrogen peroxide. A homogeneoussolution was obtained. This was allowed to stand at room temperature for24 hours. The precipitate which had formed was washed with a mixture of60 ml. acetone and 5 ml. water. The yield was 50 g., M.P. 85 C. Thefiltrate and washings were set aside for another 24 hours, when 26 gramsof the sulfoxide were deposited, M.P. 80 C., making a total of 7 6 gramsof dodecyl glyceryl sulfoxide.

Dodecyloxyethyl methyl sulfoxide, compound No. 2 of the table, wasprepared as follows: First, the monododecyl ether of ethylene glycol wasformed:

The starting product represents a dodecyl alcohol+1 mole ethylene oxideadduct. That is, by passing in one mole of ethylene oxide into one moleof dodecyl alcohol, the same product should theoretically be formed asfrom the reaction of dodecyl bromide and sodium glycol. Actually, acomplex mixture is the result, with some unchanged lauryl alcohol, andconsiderable amounts of the lauryl alcohol2 mole ethylene oxide adduct.Still, for the preparation of a bleach-stable suds booster, the

adduct would be satisfactory. The hydroxyl group was then replaced witha halogen; and this in turn replaced by a methylmercapto group; and theproduct was finally oxidized with nitric acid:

For the preparation of the monododecyl ether of ethylene glycol, 10.5 g.of metallic sodium was dissolved, a little at a time, in 250 g. of hotethylene glycol. There was then added g. of dodecyl bromide. The mixturewas refluxed four hours, cooled, and treated with water. The oil wasextracted with 500 ml. ether, and the ethereal solution sulfate. Afterremoval of the ether, the residue was fractionated. At an oil bathtemperature of 225 C., the main fiaction passed over at C./ 15 mm. Theyield was 61 g., or 66% of the theory.

To 23 g. of the monododecyl ether of ethylene glycol and 8 ml. pyridine,there was gradually added, with cool ing and stirring, 16 ml. thionylchloride. The mixture was heated on an oil bath at 100110 C. for twohours, with constant stirring. It was cooled, and excess thionylchloride decomposed with water. The oil was extracted with 200 ml.ether, the ethereal solution washed with water, then with sodiumbicarbonate solution, and again with water. The ether was distilled off,and the residue fractionated. The main fraction amounted to 17.4 g.,B.P. C./26 mm. (bath temperature 220 C.). Later it had been found thatfractionation was unnecessary. The residue after the ether evaporationwas satisfactory.

The dodecyloxyethyl chloride was converted into the sulfide thus:metallic sodium, 1.3 g., was dissolved in 60 ml. 3A alcohol, and to thiswas added 4 ml. of condensed methyl mercaptan and 12.4 g. of thechloride. The mixture was refluxed for 2 hours. Water was added, and theoil extracted with 200 ml. ether, the ether solution washed with Water,and dried with sodium sulfate. Removal of the ether left a residue whichwas distilled, B.P. 140 C./ 1.00 mm. (bath temp. 200 C.). The yield ofdodecyloxyethyl methyl sulfide was 12.1 g. This is a new compound.

The sulfide, 5.1 g., was added gradually to 12 ml. concentrated nitricacid. This was treated with ice and water, and the oil was extractedwith 100 ml. chloroform. The chloroform solution Was washed with water,sodium bicarbonate solution, again with water, and dried with anhydroussodium sulfate. The solvent was evaporated in vacuum; towards the end,25 ml. of n-hexane was added, and the evaporation continued. The yieldof dodecyloxyethyl methyl sulfoxide was 5.0 g., M.P. 43 C.

Dodecyloxyethoxyethyl methyl sulfoxide, compound No. 6 in the table, wasprepared by a procedure similar to that described for thedodecyl'oxyethyl methyl sulfoxide, according to the following equations:

C H Br C H OCH CH OCH CH OH NaBr The reaction product of monosodiumdiethylene glycol with dodecyl bromide represents the pure 100% adductof lauryl alcohol with two moles of ethylene oxide (C H OH+2ETO). Thefollowing two intermediates are new compounds:

Dodecyloxyethoxyethyl chloride,

B.P. 150 C./1.5 mm. (oil bath temp. 210 C.)

Dodecyloxyethoxyethyl methyl sulfide,

10 c n ocu cn ocmcn scn B.P. C./1.5 mm. (bath temp. 225 C.).

EXAMPLE 4 A powdered detergent composition containing the sulfoxides ofthis invention as a foam stabilizing additive was prepared to have thefollowing composition.

The following sulfoxides were separately evaluated in the above formula:dodecyl glyceryl sulfoxide, dodecyloxyethyl methyl Sulfoxide,dodecyloxyethoxyethyl methyl Sulfoxide, dodecyl Z-mercaptomethylethylsulfoxide and dodecyl acetonyl sulfoxide. The volume of foam produced inaqueous solutions of these compositions is equal or superior to thatobtained using prior art foam stabilizers. In addition, the foam remainsstable for a longer period of time than foams heretofore obtained.

What is claimed is:

1. Dodecyl 2-hydroxyethyl Sulfoxide.

References Cited UNITED STATES PATENTS 2,926,118 2/1960 Mahan 260-607 AX LEWIS GOTTS, Primary Examiner D. R. PHILLIPS, Assistant Examiner US.Cl. X.R.

